JPS6236424A - Polyorgnaosiloxane/polyoxyalkylene copolymer and its production - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a polyorganosiloxane-polyoxyalkylene copolymer, a copolymer produced by the method, and a method for using the same.

Copolymers containing siloxane and oxyalkylene units are well known and are used as surfactants in polyurethane foams and lubricants for fibers. Copolymers used as fiber lubricants have reactive groups that can be condensed to yield cross-linked polymers or polymers that are substantially bonded to the fibers. Such reactive groups are hydrolyzable groups such as alkoxy groups bonded directly to silicon atoms or via divalent groups. Fiber lubrication is Si
It is a known copolymer that has a reactive group or oxyalkylene group bonded to the siloxane chain via a -C bond, which is sufficient to sustain the effect of fiber treatment and to provide the treated fiber with the ability to remove oily stains. can be achieved. Although these copolymers are technically satisfactory in many respects, their preparation requires the use of olefinically unsaturated compounds reacted by catalytic hydrosilylation with polyorganosiloxanes containing Si-H groups. Polyoxyalkylene polymers suitable for this reaction, which entail the use of polyoxyalkylene polymers, are often expensive.

Copolymers containing siloxane units and oxyalkylene units, and having reactive groups as described above and having properties somewhat similar to the above-mentioned copolymers are cheaper oxyalkylene polymers, i.e., Si-H groups. It has been found that it can be produced using polyorganosiloxanes having hydroxyl groups that can react with polyorganosiloxanes having hydroxyl groups.

In these copolymers, the polyoxyalkylene group is S
i -0-C bonds to the siloxane chain and, surprisingly, these compounds are highly hydrolyzed to withstand use in textile processing where they are repeatedly exposed to harsh hydrolytic conditions. Sufficiently stable against degradation.

The present invention provides a method for producing a polyorganosiloxane-polyoxyalkylene copolymer having at least one hydrolyzable group, and its features are as follows. That is, (1) Si-
A polyorganosiloxane having an H group is reacted with a stoichiometrically small amount of a monoether of a polyoxyalkylene glycol in the presence of a catalyst, and (2) the reaction product has the general formula L SiA a(OA ′ >3-a
(wherein, L is an aliphatic group having 2 to 8 carbon atoms and an olefinically unsaturated group, A is independently an alkyl group having 1 to 8 carbon atoms, and A' is C1H and optionally a group with 0 atoms, a indicates 0.1 or 2, OA' indicates a hydrolysable group, and the amount of silane is determined by hydrosilylation.
lation) In the presence of a catalyst, residual unreacted Si-H
in an amount sufficient to react with the group. ), in this way a polyorganosiloxane-polyoxyalkylene copolymer is produced, which contains SiO-C in the SiH atoms of the siloxane chain.
6 SiH groups having 25-75% by weight of the total copolymer amount of polyoxyalkylene groups bonded via bonds and at least one hydrolyzable group bonded to another Si atom; Polyorganosiloxanes, also referred to as hydrosiloxanes, are suitable for use in the process of the present invention, but their preparation is well known to those skilled in the art. These typically have the following general formula:

Here, R is independently an alkyl or allyl group having 1 to 8 carbon atoms, X and y are x+y about 50 to 500, y/
The choice is such that X+y is 0.01 to 0.5, and y is at least 2. Preferably at least 50
% of the Rf substituents are methyl groups, and more preferably substantially all R are methyl groups. Any other substituents are selected from ethyl, propyl, isobutyl, or phenyl groups. The preferred range for +y is from 80 to 250, most preferably from about 100 to 180.

The ratio of y/to+y is preferably about 0.1 to 0.2. These values are average values and some hydrosiloxanes may have values outside this range.

In a preferred example of a hydrosiloxane used in the method of the invention, the values of x+y and y/x+y are as follows.

"Earthwork" Z ME±L 98 0.122 148 0.203 164 Q, 116 Monoethers of polyoxyalkylene glycols suitable for use in the present invention are those having the following general formula.

HO-(CnH2nO)zR' where R' is an alkyl, allyl, alkaryl, aralkyl or acyl group having 1 to 8 carbon atoms, and n is 2 to 8
, where 2 has an average value of at least 2.

The use of the monoether rather than the polyoxyalkylene glycol directly is important. This is because when a polyoxyalkylene glycol monoether reacts with a hydrosiloxane, the end groups of the polyoxyalkylene are not reactive, and the silane used to react with the remaining SiH groups is then
This is because it can react with this SiH instead of polyoxyalkylene.

R' is preferably a lower alkyl group and most preferably a methyl group. The monoether of polyoxyalkylene glycol is preferably one in which n is 2 or 3, most preferably one in which all oxyalkylene groups are oxyethylene groups. Monomethyl ether of polyoxyethylene glycol is most preferred.

As long as the oxyalkylene group of the polyorganosiloxane-polyoxyalkylene copolymer is 25 to 75% by weight of the total copolymer, the value of 2 does not have to be strict; preferably, the value of 2 is 6 to 15. The most preferred raw materials will have a molecular weight of about 300-700. Preferred examples of these polyoxyethylene glycol monoethers have molecular weights of about 350 (z is 7.2) or about 550
(z is 11.8) The hydroxyl group of the monoether of the polyoxyalkylene suitable for use in the method of the present invention reacts with the SiH group of the hydrosiloxane to form a polyoxyalkylene group bearing R', and Si- Si with 0-〇 bond
Monoethers of polyoxyalkylene glycols suitable for use in the process of the present invention bonded to atoms include allyl (a
llyl) substituted hydroxypolyoxyalkylenes or their ethers. These produce similar corresponding copolymers, but with the oxyalkylene group
It is bonded to the Si atom via Si-C. The amount of polyoxyalkylene glycol monoether reacting with hydrosiloxane is 25 to 75 ffi of the total copolymer amount.
jt% is an oxyalkylene group. However, the amount should be smaller than the amount required to react with all SiH groups. Preferably, at least one SiH group of each hydrosiloxane molecule remains unreacted with the polyoxyalkylene glycol monoether. Most preferably, two SiHs remain.

The reaction of hydrosiloxane with monoether of polyoxyalkylene glycol is carried out in the presence of a catalyst. Such catalysts are well known, for example Ba(O
H)2. Sr(OH)2. , Na2SiOa.

Na2CO3, SrCO3, Ca(OH)2. BaCO
2°M g(OH)2, MgCO3, or a platinum complex.

Particularly suitable catalysts include 2Co3,
The reaction rate is high. The catalyst for this reaction is effective in an amount of, for example, about 0.5 to 5% of the total amount of reactants. Most of these catalysts are particularly advantageous since they can be separated from the reaction mixture by filtration.

Silanes suitable for use in the process of the invention can have alkoxy, alkoxyalkoxy, allyloxy or acyloxy groups as hydrolysable groups.

The unsaturated group represented by is preferably a vinyl or allyl group. Suitable silanes for use in the process of the invention are those where a is zero, A' is alkyl, and L is vinyl.

The most preferred silane is vinyltrimethoxysilane.

These silanes react with the SiH groups remaining in the hydrosiloxane after the hydrosiloxane has reacted with the monoether of the polyoxyalkylene glycol. This reaction is carried out in the presence of a hydrosilylation catalyst. Suitable catalysts for this reaction are, for example, platinum-containing catalysts such as H2p tC+6.xH2O.

Although all SiH groups of the hydrosiloxane are preferably reacted with the polyoxyalkylene glycol monoether or silane, trace amounts of unreacted SiH may remain in the copolymer.

Both reactions are preferably carried out under substantially anhydrous conditions and in the presence of a solution that is inert to all reactants; a particularly suitable solvent is toluene. It is important that the reaction between the hydrosiloxane and the monoether of polyoxyalkylene glycol is carried out until completion, after which the hydrosilylation reaction between the SiH remaining in the hydrosiloxane and the silane begins. If the order is reversed or the silane is added before the first reaction is complete, the monoether of the polyoxyalkylene glycol may react with the hydrolyzable groups present in the silane, resulting in As a result, a copolymer having the desired composition cannot be obtained.

The polyorganosiloxane-polyoxyalkylene copolymer obtained by the method of the present invention has a total amount of 25 to 25% of the total amount bonded to the Si atoms of the siloxane chain via Si-0-C.
It has 75% by weight polyoxyalkylene groups and at least one hydrolyzable group bonded to a different Si atom. These copolymers are particularly useful as fiber treatment agents.

The presence of at least one hydrolyzable group per molecule means that the copolymer can react by hydrolysis with other reactive groups, for example on fibers or on other silicon molecules. .

This reaction is shown below.

)SiOA′+H20→)SioH+A” 0H)S
i-OH+HO-3iku-)Si-0-3i(+H20
-)SiOH+HOC-textile-+)Si-
0-C(-textile+H20) It remains as a copolymer finish on the fiber and is resistant to laundering with surfactants.Other advantages when crosslinking of this copolymer occurs are e.g. It imparts elastic finish properties to the fibers, such as improving recovery.

To obtain this result, the number of Si atoms in the siloxane backbone structure of the polyorganosiloxane is preferably at least 50 (i.e. x + y = 48>). Alternatively, it can be applied to the fibers afterwards.

Copolymers of the present invention having 25 to 75% by weight polyoxyalkylene have a more improved oily soil release effect than those with lower amounts of polyoxyalkylene. Preferred polyorganosiloxane-polyoxyalkylene copolymers have sufficient oxyalkylene in them to make the copolymer water-dispersible, and most preferably have enough oxyalkylene to make the copolymer water-soluble. It has sufficient oxyalkylene content. In this way, the copolymer can be applied onto the fiber material, for example from the state of an aqueous solution. The Si-0-C bonds linking the polyoxyalkylene groups to the siloxane skeleton are surprisingly stable under conditions where hydrolysis occurs. The most preferred polyorganosiloxane-polyoxyalkylene copolymers have at least about 40% by weight of the total copolymer oxyalkylene groups. The amount of oxyalkylene in the copolymer is 75% based on the texture of the treated fibers.
It is preferable not to exceed % by weight.

If this amount is too large, the fibers will feel loose to the touch, which is undesirable.

The molecular weight of the copolymers of the present invention should be large enough to improve the hand feel of the treated fibers. Preferred molecular weights are at least 3,000, and most preferably at least 5,000.

The polyorganosiloxane-polyoxyalkylene copolymer of the present invention can be applied in the form of an aqueous solution, an alcoholic solution or a dispersion by conventional fiber treatment methods such as the padding dipping method.

A condensation catalyst may be added to the solution or dispersion.
These catalysts are well known to those skilled in the art and include, for example, tin salts and amino functional materials. An example of a suitable catalyst is dibutyltin bis(lauryl) mercaptide. These catalysts can be added in an amount of about 0.5 to 10% by weight based on the weight of the polyorganosiloxane-polyoxyalkylene copolymer.

This copolymer can be applied to the fibers in an amount of 0.1 to 5% by weight of the fibers. However, when applied to fibers, a zero-strand copolymer that provides good stain release properties, hand feel, and long-lasting effects when added at about 1% by weight, when heated to a sufficiently high temperature such as 150°C, Crosslinking occurs by condensing the Si--OH groups.

Next, 0 parts shown in Examples of the present invention are parts by weight unless otherwise specified. Me represents -CH3.

Fully detailed stirrer, thermometer, Dean and Stark apparatus (
Dean and S Lark upper
2000 g into a 5 X 10-3++' split flask (aplitflask) equipped with
of dry toluene and 1040. of polyoxyethylene monoethyl ether (average molecular weight 1551) was added.

The contents of the flask were stirred and heated to reflux, and the water in the ether was removed azeotropically, and 2.7 ci+' of water was collected. The Dean and Stark device was replaced with a reflux condenser. Inert gas was introduced into the flask.

16.81F finely ground potassium carbonate was placed in a flask and heated to 80"C with vigorous stirring.7
A hydropolysiloxane with an average composition of 21.8 fI was slowly added to the flask.

Me3S i(OS iMe2)++6(OS iMe
H)3(10S iMe3 reaction mixture evolved hydrogen. The temperature was kept at 80 °C until hydrogen evolution stopped after all the hydrosiloxane was added. The total reaction time was about 5 hours. The contents were cooled to 25°C and the potassium carbonate was removed in one pass. 0.33 cm3 of a 10% by weight solution of H2PtCIs.XH2O in isopropanol was added to the flask and heated to 80'C without stirring. I did.2
Add 0g of vinyl trimethylsiloxane to the mixture;
When the reaction mixture kept at 80°C for 1 hour was examined by infrared spectroscopy, -3iH was not detected. Toluene was removed from the flask under reduced pressure of 7×10 2 Pa at a maximum temperature in the flask of 83°C.

In this way, the polyorganosiloxane of the first embodiment
Polyoxyalkylene copolymer 1617. was gotten.

It is a clear, amber colored liquid with a temperature of 310 mP at 25°C.
The viscosity was a-5. The methoxy group of this copolymer is
The theoretical value was 3.99% by weight, but the analytical value was 3.77% by weight. The amount of oxyethylene is 55% in the total polymer.
1% by weight. The average composition of the product is believed to be:

Hydrosiloxane Me3Si (
O3iMe2)+4s(OSiMeH)+903iM
Example 1 was carried out in the same manner as in Example 1, except that 40.4 parts of e3 and 31.4 parts of polyoxyethylene glycol monoether (molecule 1551) were reacted and vinyltrimethoxysilane was subsequently reacted.

The copolymer of this second example had an oxyalkylene content of 40.7% by weight and a methoxy content of 2.68% by weight (calculated value 2.86% by weight).

The average composition of this copolymer is as follows.

Hydrosiloxane Me:iS having the following average composition:
i (OS iMe2) 14! i(OS iMeH)1
40.4 parts of go SiMe3 was added to monomethyl ether of polyoxyethylene glycol (molecular weight 350).
The procedure of Example 1 was followed, except that the reaction was carried out with 18.8 parts of silane and 1 part of vinyltrimethoxysilane.

The copolymer of this third example had an oxyalkylene content of 2
9.6% by weight, methoxy group 2.8% by weight (calculated value 3.8
%), which had the following average composition:

Hydrosiloxane Me3S i with the following average composition:
(OS iMe2) as (OS iMeH) tzo S
24.3 parts of iMe3 and 18.5 parts of monomethyl ether of polyoxyethylene glycol (molecular weight 551)
A polyorganosiloxane-polyoxyalkylene copolymer of Example 4 was prepared in the same manner as in Example 1, except that 1 part of vinyltrimethoxysilane was reacted with 1 part of vinyltrimethoxysilane.

The copolymer of this fourth example had an oxyalkylene content of 39.8% by weight and a methoxy group content of 2.52% by weight (calculated value of 3.5%). It had the following average composition:

Three fiber samples consisting of a 65/35 polyester/cotton blend lightweight shirting fabric, undyed and scoured, were processed as follows.

The first fiber sample was treated with a 40% aqueous emulsion of a high molecular weight, silanol-terminated polydimethylsiloxane liquid using the padding method to 1% by weight of 11 fibers. At the same time, pre-hydrolyzed methyltrimethoxysilane and dibutyltin bis(lauryl) mercaptide were also applied. The siloxane:silane:tin salt ratio is 20
: The ratio was 1:2.

The second fiber sample was treated by a padding method using an aqueous solution of the polyorganosiloxane-polyoxyalkylene copolymer of the first example in an amount of 1% by weight based on the weight of the fiber. At the same time, an emulsion of dibutyl i(lauryl) mercaptide was also applied. Copolymer: tin salt ratio is 1:0.05
Met.

A third fiber sample was left untreated.

After drying, these three types of fiber samples were dried using a stenter.
The mixture was cured for 3 minutes at 150° C.

The first and second fiber samples were much smoother and softer to the touch than the third.

0.5 cz" of water is placed on the sample as a water drop,
The water-wetting property was measured by measuring the time until it became completely wet. The results are shown in Table 1.

[IJL 1st sample 123.3 2nd sample 35.5 3rd sample 89.0 Next, to measure the sustainability of the treatment, all samples were heated at 60°C.
I put it through 5 cycles in an automatic washing machine. After drying, the fiber samples are freed from the following oily contaminants: butter, liquid paraffin,
Soiled with olive oil and mayonnaise. All samples were then subjected to an oil stain release test according to AATCC Test Method 130. The results are shown in Table 2.

(1 indicates no removal of dirt, 5 indicates complete removal of dirt.) 1st sample 3.5 1.75 2.75
2.5 Second sample 3.75 3.75 4
．． 5 4.25 Third sample 3.5 2.75
3.5 3 As can be seen from the above test results, the fiber samples treated with the copolymer of the present invention have better hand feel, longer lasting treatment effect, better hydrophilicity, and better This shows the releasability of oily stains.

Claims (1)

[Claims] 1. A polyorganosiloxane-polyoxyalkylene having a polyoxyalkylene group bonded to a Si atom of a siloxane chain and at least one hydrolyzable group bonded to another Si atom. In the copolymer, the polyoxyalkylene group connects to Si through Si-O-C bonds.
A polyorganosiloxane-polyoxyalkylene copolymer, characterized in that it is bonded to atoms and accounts for 25 to 75% by weight of the total amount of the copolymer. 2. The polyorganosiloxane-polyoxyalkylene copolymer according to claim 1, wherein the copolymer has a molecular weight of at least 5,000. 3. In the production of a polyorganosiloxane-polyoxyalkylene copolymer having at least one hydrolyzable group, (1) polyorganosiloxane having an Si-H group is stoichiometrically mixed in the presence of a catalyst. (2) react this reaction product with the general formula LSiAa (OA'
)_3_-_a (wherein, L is an aliphatic group having 2 to 8 carbon atoms and an olefinically unsaturated group, A is independently an alkyl group having 1 to 8 carbon atoms, and A ′
is a group having C, H and optionally O atoms, a
represents 0, 1 or 2, OA' represents a hydrolyzable group, and the amount of silane is determined by hydrosilylation (hydrosilylation).
osilylation) in an amount sufficient to react with residual unreacted Si-H groups in the presence of a catalyst. ), in this way a polyorganosiloxane-polyoxyalkylene copolymer is produced, which has S attached to the Si atom of the siloxane chain.
having 25 to 75% by weight of the total copolymer amount of polyoxyalkylene groups bonded via i-O-C bonds, and at least one hydrolyzable group bonded to another Si atom; A method for producing a polyorganosiloxane-polyoxyalkylene copolymer, comprising: 4. The manufacturing method according to claim 3, wherein the polyorganosiloxane having Si-H groups has the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, R is independently an alkyl or allyl group having 1 to 8 carbon atoms, x and y are x + y of about 50 to 500,
y/x+y is chosen such that 0.01 to 0.5 and y is at least 2. )5, x+y is about 10
0 to 180, and y/x+y is 0.1 to 0.2, the manufacturing method according to claim 4. 6. The manufacturing method according to claim 3, wherein the polyoxyalkylene monoether has the following general formula. HO-(CnH_2nO)_2R' (wherein, R' is an alkyl, allyl, alkaryl, aralkyl, or acyl group having 1 to 8 carbon atoms, and n is 2 to 8 carbon atoms.
8, z has an average value of at least 2. 7. The manufacturing method according to claim 6, wherein the monoether of polyoxyalkylene glycol is monomethyl ether of polyoxyethylene glycol. 8. The manufacturing method according to claim 6, wherein the monoether of polyoxyalkylene glycol has a molecular weight of about 300 to 700. 9. The manufacturing method according to claim 3, wherein the silane is vinyltrimethoxysilane.